CN101668786B - Curable resin composition, led package, and method for production of the led package, and optical semiconductor - Google Patents
Curable resin composition, led package, and method for production of the led package, and optical semiconductor Download PDFInfo
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- CN101668786B CN101668786B CN2008800132963A CN200880013296A CN101668786B CN 101668786 B CN101668786 B CN 101668786B CN 2008800132963 A CN2008800132963 A CN 2008800132963A CN 200880013296 A CN200880013296 A CN 200880013296A CN 101668786 B CN101668786 B CN 101668786B
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- Prior art keywords
- curable resin
- resin composition
- mentioned
- mass parts
- isocyanic ester
- Prior art date
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
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Abstract
The curable resin composition of the present invention comprises a polyol component containing tri- or higher functional polycaprolactone polyol; and a polyisocyanate component containing bifunctional or trifunctional alicyclic isocyanate having one or more chemical structures in which an isocyanate group is bonded to a secondary carbon atom.
Description
Technical field
The present invention relates to curable resin composition, photodiode (Light Emitting Diode; LED) packaged piece and method of manufacture thereof.In addition; The curable resin composition that optical characteristics such as the optical transparence that the present invention relates to its cured article is high, heat-resisting, coloring resistance or mechanical characteristics are superior and used photosemiconductors such as the superior photodiode (LED) of the safety of said cured article, phototransistor, photodiode, solid-state imager.
Background technology
In the past, the usually transparency or superior acrylic resins of photostabilization of using in the used for optical part resin more.In addition, the used for optical part resin that utilizes in the photoelectronic device field is required installation procedure or thermotolerance under the hot operation or mechanical characteristics to electric substrate etc., therefore, using epoxy usually is resin.
In recent years, in the purposes of photoelectronic device field, the utilization of high-intensity laser, blue light or near-ultraviolet light also enlarges, and follows in this, seeks superior resins such as the transparency, thermotolerance, photostabilization in the past abovely.Also have, epoxy resin has the high transparency in the visible region, but from ultraviolet to the near-ultraviolet light zone, can not get the sufficient transparency.Wherein, the transparency of epoxy resin of having used ester ring type dihydroxyphenyl propane diglycidyl ether etc. is than higher, but exists because heat or problems such as light and easy colorizing.
Therefore, for example, the method as the impurity of one of coloration reason that reduces in ester ring type dihydroxyphenyl propane diglycidyl ether, to contain is disclosed in patent documentation 1,2.
Yet, from now on, will seek further raising to thermotolerance and ultraviolet coloring resistance property, can't say enough through the scheme of record in the above-mentioned patent documentation 1,2.
In addition, as the transparent superior resin system of cured article near ultraviolet region, know the material that obtains by alicyclic epoxy resin and acid anhydrides.Also have, the breaking tenacity of this cured article and toughness are than poor based on the material of aromatic epoxy resin, therefore, in the forming composition insufficient with interface peel or crackle the xenogenesis conjugant.In addition, with regard to this resin system, acid anhydrides volatilization when solidifying, the aspect of volume reducing also has problems.
On the other hand, the transparency of acrylic resin is high, be difficult to because light or heat and painted coloring resistance property is superior, but that mechanical characteristicies such as breaking tenacity we can say is insufficient, seeks the raising of further characteristic.In addition, the cure shrinkage of this resin system is bigger, and the volume reducing during curing is remarkable.
On the other hand, the transparency of silicone resin till near ultraviolet region is high, and the combination energy of Si-O is big, therefore, has: have superior photostabilization, be difficult to because heat or light and painted characteristic.Usually, silicone resin is through the condensation reaction between the dehydration condensation between the silanol group or silanol group and the water-disintegrable base, wait polymerization based on the addition reaction of reaction, vinyl silyl and the hydrogen silyl of the organo-peroxide of methyl-silicane base and vinyl silyl.
For example, in patent documentation 3, the silicone resin that the addition reaction through vinyl silyl and hydrogen silyl obtains is disclosed.
Yet; The influence of the poisoning of catalyst that causes owing to curing atmosphere when the silicone resin that obtains of the addition reaction that utilizes vinyl silyl and hydrogen silyl of record in above-mentioned patent documentation 3 has and the curing that do not make progress, or problem such as the thermal expansivity of cured article is big.
On the other hand, the urethane resin that the reaction through NCO and hydroxyl obtains has especially used heat-resisting, the fast light tint permanence of urethane resin of ester ring type isocyanic ester superior, therefore, as open in the patent documentation 4, it is used resin as optical lens shaping.In addition, in patent documentation 5, the example of the components of photo-electric conversion sealing material use urethane based resin composition that has used aliphatics or ester ring type polymeric polyisocyanate is disclosed.
Patent documentation 1: the spy opens the 2003-171439 communique
Patent documentation 2: the spy opens the 2004-075894 communique
Patent documentation 3: the spy opens the 2004-186168 communique
Patent documentation 4: the spy opens the 2003-301025 communique
Patent documentation 5: the spy opens the 2001-278941 communique
As the used for optical part resin combination; The resin combination of expecting solvent-free system is promptly at room temperature for liquid; The cure shrinkage of its cured article is little, optical characteristics such as the transparency, photostabilization, thermotolerance, and the resin combination of the superior suitable optics of mechanical characteristics such as breaking tenacity.
Also have, LED with sealing resin in for the reduction of the brightness that suppresses LED, the especially superior transparency, photostabilization and the thermotolerance of needs.In addition,, temperature cycling test and hot and humid some lantern test are arranged,, also need high mechanical characteristics and high-temp resisting high-humidity resisting property for clear and definite these tests in order to estimate the safety of LED packaged piece.
Yet; For example the disclosed urethane resin that has used the polymeric polyisocyanate of NCO and primary carbon adjacency is used under the situation of sealing of LED among the embodiment with patent documentation 5; If shown in comparative example 4 of the present invention; Carry out the continuity point lantern test under the hot and humid condition, then have the problem of following brightness to reduce.
As using liquid heat-curing resin, the method for sealing LED is used casting resin in mold usually, is heated solidified casting moulding method.Yet, in the method, exist the curing of heat-curing resin slow, produce the problem of rate variance.In addition, be difficult to control the thickness of sealing resin, or in sealing resin, sneak into the space easily.
In recent years, follow the expansion in the market of LED, seeking to improve the LED packaged piece production process of the property produced in batches.From such viewpoint, at room temperature in the die cavity of heated die, be pressed into liquid resin combination, the molding cycle that to make its moulding method that is heating and curing be liquid transfer mould or compression molding is short, and productivity is high, and is therefore useful.In addition, if use these moulding method, then can also give shape arbitrarily to sealing resin.In order to be suitable for said liquid transfer mould, make the LED packaged piece, need have the resin combination of the curing speed that matches with its condition of moulding.
Summary of the invention
The present invention In view of the foregoing makes, and its first purpose is to provide the curable resin composition that especially can form the superior fully cured article of high-temp resisting high-humidity resisting property, LED packaged piece and the method for manufacture thereof of using said resin combination to make.
And then usually, the second-order transition temperature of urethane resin is low, therefore, as after shown in the comparative example 4～8 stated, in temperature cycling test, exist the displacement of metal wire big, the problem of broken string takes place.Thereby, expect solvent-free system and in room temperature (25 ℃) down for liquid, optical characteristics, mechanical characteristics such as transparent or fast light, the heat-resisting tint permanence of cured article and be used under the situation of sealing of optical semiconductor the resin combination that safety is superior.
The present invention In view of the foregoing makes; Its second purpose is to provide the superior curable resin composition of optical characteristics such as the transparency of its cured article is high, heat-resisting, fast light tint permanence or mechanical characteristics and has used photosemiconductors such as the superior photodiode (LED) of the safety of said cured article, phototransistor, photodiode, solid-state imager.
In order to realize above-mentioned first purpose, the present invention provides following first curable resin composition, LED packaged piece and method of manufacture thereof.
The present invention provides a kind of curable resin composition, it is characterized in that, contains: polyhydroxy reactant, and it contains the above polycaprolactone polyol of trifunctional; The polymeric polyisocyanate composition, it is to contain the ester ring type isocyanic ester that the chemical structure that NCO is incorporated into secondary carbon(atom) has more than one two functional groups or trifunctional more than the 40 quality %.
In addition, the present invention provides a kind of curable resin composition, wherein, contains: polyhydroxy reactant, and it is so that to contain weight-average molecular weight more than the 40 quality % be below 800 and hydroxyl value is the polycaprolactone polyol more than the trifunctional more than the 200mgKOH/g; The polymeric polyisocyanate composition, it contains the ester ring type isocyanic ester that the chemical structure that NCO is incorporated into secondary carbon(atom) has more than one two functional groups or trifunctional.
Just possess the curable resin composition of the present invention of above-mentioned formation,, also suppress the reduction of brightness fully even the photodiode that uses this resin combination to make is exposed under the hot and humid condition.The reason that can form such cured article that especially high-temp resisting high-humidity resisting property is superior fully is also concrete so far clear and definite.Yet the inventor etc. think that one of its reason is the factor of following record.But reason is not limited to this.
Promptly; The polyvalent alcohol composition of the polycaprolactone polyol in the curable resin composition more than containing the trifunctional that in a molecule, has three above hydroxyls; As the polymeric polyisocyanate composition; Contain the ester ring type isocyanic ester that the chemical structure that NCO is incorporated into secondary carbon(atom) has more than one two functional groups or trifunctional; Compare with the situation that contains the ester ring type polymeric polyisocyanate with such chemical structure thus, the high-temp resisting high-humidity resisting property of cured article improves fully.And then through in whole polymeric polyisocyanate compositions, containing such ester ring type isocyanic ester more than with 40 quality %, the high-temp resisting high-humidity resisting property of cured article uprises more fully.Equally, in whole polyhydroxy reactants, containing weight-average molecular weight more than with 40 quality % is below 800 and hydroxyl value is the polycaprolactone polyol more than the trifunctional more than the 200mgKOH/g, and the high-temp resisting high-humidity resisting property of cured article also uprises more fully.
In addition, the cured article of curable resin composition of the present invention has the high transparency, and, can its curing speed be adjusted to the speed that matches with liquid transfer mould.Therefore, this curable resin composition is useful in the situation of utilizing liquid transfer mould to make light emission diode package member, and its cured article is suitable as the effective transparent sealing resin of light-emitting diodes fully.
Gelation time under preferred 165 ℃ of the curable resin composition of the present invention is 10～200 seconds.Thus; Can be in that (raw material that will at room temperature be solid-state shape be behind in-pot melting with in the past solid-state transfer mould; The fused raw material is pressed in the die cavity of mould; Make its solidified method of forming) under the roughly the same condition of molding, carry out making based on the light emission diode package member of liquid transfer mould, improve the efficient that packaged piece is made.
At this, the time that " gelation time " among the present invention is to use commercially available gelation trier to measure.More particularly, upload the curable resin composition of putting 0.2g, utilize semicure method (Ha Application De キ ユ ア) to measure at the hot plate that is heated to be 165 ℃.
In curable resin composition of the present invention, the preferred polyol composition contains: obtain, the residual prepolymer that hydroxyl is arranged of isocyanate reaction more than two functional groups of the NCO of the sum that make polyvalent alcohol, lacks with the sum with the hydroxyl that has than this polyvalent alcohol.Contain said prepolymer through polyhydroxy reactant, the curing speed of curable resin composition further accelerates, and is more suitable for liquid transfer mould.In addition, through containing such prepolymer, the consistency of polyhydroxy reactant and polymeric polyisocyanate composition further improves.And then, can also play contribution to the reduction of the cure shrinkage of curable resin composition.
From same viewpoint; What be fit to is that the polymeric polyisocyanate composition contains: obtain, the residual prepolymer that NCO is arranged of polyol reaction of the hydroxyl of the sum that make the above isocyanic ester of two functional groups, lacks with the sum with the NCO that has than this isocyanic ester.
Curable resin composition of the present invention preferably contains from improving sunproof viewpoint: the type phenol of being obstructed is inhibitor.
The present invention provides the light emission diode package member that possesses the sealing element that the above-mentioned curable resin composition of curing molding obtains.Adopt the cured article of curable resin composition of the present invention in this light emission diode package member as sealing element, the high-temp resisting high-humidity resisting property of sealing element is superior fully, therefore, in hot and humid some lantern test, can keep high brightness for a long time.Such light emission diode package member can utilize liquid transfer moudling with above-mentioned curable resin composition curing molding through having, and the method for manufacture that obtains the operation of sealing element is made.Can know according to this method of manufacture, can make above-mentioned light emission diode package member with high productivity.
In order to realize above-mentioned second purpose, the present invention provides following second curable resin composition, and photosemiconductor.
The present invention provides a kind of curable resin composition, wherein, contains: polyhydroxy reactant; The polymeric polyisocyanate composition; It contains the chemical structure that NCO is incorporated into secondary carbon(atom) and has the isocyanuric acid ester type isocyanic ester more than more than one two functional groups; The second-order transition temperature of the cured article of said curable resin composition is more than 110 ℃, and the thermal expansivity when second-order transition temperature is following is 10.0 * 10
-5/ ℃ below, the thermal expansivity when second-order transition temperature is above is 20.0 * 10
-5/ ℃ below, and the bending elastic modulus under 25 ℃ is more than the 1500MPa.
In curable resin composition of the present invention; Preferred said polyhydroxy reactant is so that to contain weight-average molecular weight more than the 40 quality % be below 500 and hydroxyl value is the polycaprolactone polyol more than the trifunctional more than the 300mgKOH/g; And to contain weight-average molecular weight more than the 30 quality % be below 350, hydroxyl value is the aliphatic polyol more than the trifunctional more than the 500mgKOH/g, said polymeric polyisocyanate composition is to contain said isocyanuric acid ester type isocyanic ester more than the 40 quality %.
At this, the preferred TriMethylolPropane(TMP) or derivatives thereof of above-mentioned aliphatic polyol.
In curable resin composition of the present invention, preferred said isocyanuric acid ester type isocyanic ester is the Trimerization of Isophorone Diisocyanate thing.
In curable resin composition of the present invention, preferred said polyhydroxy reactant contains: obtain, the residual prepolymer that hydroxyl is arranged of isocyanate reaction more than two functional groups of the NCO of the sum that make polyvalent alcohol, lacks with the sum with the hydroxyl that has than this polyvalent alcohol.
At this, the above-mentioned prepolymer in the preferred above-mentioned polyhydroxy reactant is that to make the ratio (X/Y) of said polyvalent alcohol and said isocyanic ester hydroxyl equivalent X and the NCO equivalent Y in the said isocyanic ester in said polyvalent alcohol be that reaction obtains under the condition more than 3.
In curable resin composition of the present invention, preferred said polymeric polyisocyanate composition contains: obtain, the residual prepolymer that NCO is arranged of polyol reaction of the hydroxyl of the sum that make the above isocyanic ester of two functional groups, lacks with the sum with the NCO that has than this isocyanic ester.
At this, preferred said polyvalent alcohol is that weight-average molecular weight is below 350 and hydroxyl value is the above aliphatic polyol of the above trifunctional of 500mgKOH/g.
In addition, the said prepolymer in the preferred said polymeric polyisocyanate composition is that to make the ratio (X/Y) of said polyvalent alcohol and said isocyanic ester hydroxyl equivalent X and the NCO equivalent Y in the said isocyanic ester in said polyvalent alcohol be to react under 0.05～0.30 the condition to obtain.
Curable resin composition of the present invention preferably contains: the type phenol of being obstructed is inhibitor.
At this, the preferred said type phenol that is obstructed is that inhibitor is 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.
Gelation time under preferred 165 ℃ of the curable resin composition of the present invention is 10～200 seconds.
In the preferred curable resin composition of the present invention,, the ratio of the NCO equivalent in hydroxyl equivalent in the said polyhydroxy reactant and the said polymeric polyisocyanate composition (hydroxyl equivalent/NCO equivalent) contains said polyhydroxy reactant and said polymeric polyisocyanate composition so that becoming 0.7～1.3 mode.
The present invention and then a kind of photosemiconductor is provided wherein, possesses: utilize liquid transfer moudling, the parts that the curable resin composition moulding of the invention described above is obtained.
Can know according to the present invention, first curable resin composition that especially can form the superior fully cured article of high-temp resisting high-humidity resisting property, LED packaged piece and the method for manufacture thereof of using said resin combination to make can be provided.In addition, the transparency that second curable resin composition of the present invention has its cured article is high, and fast light, heat-resisting optical characteristics such as painted or mechanical characteristics are superior, and simultaneously, second-order transition temperature is high, and the low characteristic of thermal expansivity.Therefore, under the situation of the sealing resin that is used as optical semiconductor, be difficult to the broken string in the occurrence temperature round-robin test, can improve the life-span or the safety of optical semiconductor.
Description of drawings
Fig. 1 is the constructed profile of the light emission diode package member of expression suitable embodiment of the present invention.
Fig. 2 is the constructed profile of the light emission diode package member of expression other embodiments of the present invention.
Among the figure: the 1-substrate; The 2-wiring layer; The 22-lead frame; 3,23-adhering part; 4,24-light-emitting diode; 5,25-metal wire; 6,26-sealing element; 10,20-light emission diode package member; The 27-box part.
Embodiment
Below, in the time of as required with reference to accompanying drawing, specify suitable embodiment of the present invention.Also have, in the drawings, for identical important document, the mark same-sign is omitted repeat specification.In addition, wait the position relation not limit especially up and down, based on position shown in the drawings relation.And then the dimension scale of accompanying drawing is not limited to illustrated ratio.
(first curable resin composition)
At first, first curable resin composition of the present invention is described.First curable resin composition of the present invention contains: polyhydroxy reactant, and it contains the above polycaprolactone polyol of trifunctional; The polymeric polyisocyanate composition, its contain with NCO be incorporated into secondary carbon(atom) bonded chemical structure have more than one two functional groups or trifunctional the ester ring type isocyanic ester (below, be called " specific ester ring type isocyanic ester ".)。
The curable resin composition of said first embodiment suitably contains: the polyhydroxy reactant that contains the above polycaprolactone polyol of trifunctional; To contain the polymeric polyisocyanate composition of specific ester ring type isocyanic ester more than the 40 quality %.
In addition, the curable resin composition of the second suitable embodiment contains: polyhydroxy reactant, and it is so that to contain weight-average molecular weight more than the 40 quality % be below 800 and hydroxyl value is the polycaprolactone polyol more than the trifunctional more than the 200mgKOH/g; The polymeric polyisocyanate composition, it contains specific ester ring type isocyanic ester.
Polyhydroxy reactant of the present invention contains the above polycaprolactone polyol of trifunctional.As this polycaprolactone polyol, the polycaprolactone polyol that can enumerate trifunctional is polycaprolactonetriol, the polycaprolactone polyol that reaches four-functional group.Contain the polycaprolactone polyol more than the trifunctional through polyhydroxy reactant, obtain the cross-linking density height, the effect that the hardness of cured article or obdurability are high.
Utilize the above polycaprolactone polyol of the synthetic trifunctional of usual method also can, obtain commercially available material and also can.As the polycaprolactone polyol more than the commercially available trifunctional, for example, can enumerate trade(brand)name " pula Ke Xier (プ ラ Network セ the Le) " series of wearing West Road (ダ イ セ Le) chemical company's system.
The above polycaprolactone polyol of trifunctional can use a kind of separately or make up two or more uses.
In second embodiment, the weight-average molecular weight of the polycaprolactone polyol that trifunctional is above is below 800 and hydroxyl value is more than the 200mgKOH/g, the result that the cross-linking density when solidifying thus uprises fully, and the hardness or the obdurability of cured article uprise fully.From the viewpoint of the reduction of the hardness of further inhibition cured article and obdurability, the weight-average molecular weight of the polycaprolactone polyol that trifunctional is above and then preferred below 500, hydroxyl value and then more than the preferred 300mgKOH/g.
The preferred polyol composition contains to be made polyvalent alcohol and has obtain, the residual prepolymer that hydroxyl is arranged of isocyanate reaction more than two functional groups of NCO of the sum that the sum of the hydroxyl that has than this polyvalent alcohol lacks.This prepolymer is the isocyanic ester radical reaction through hydroxyl groups and isocyanic ester, generates urethane bond and obtains.Through containing this prepolymer, the curing speed of curable resin composition and then accelerate, therefore, said compsn is more suitable for liquid transfer mould.In addition, contain said prepolymer through polyhydroxy reactant, the intermiscibility of polyhydroxy reactant and polymeric polyisocyanate composition improves, and the degree of cure shrinkage reduces.In this case, polyvalent alcohol can be the polycaprolactone polyol more than the trifunctional, also can be polyvalent alcohol in addition.
When synthetic above-mentioned prepolymer, the preferred X/Y of ratio of the sum (X) of the hydroxyl that has as the polyvalent alcohol of raw material and the sum (Y) of the NCO that isocyanic ester has becomes 3～20.If X/Y surpasses 20, then use prepolymer and the above-mentioned effect that plays reduces, be in the tendency of the advantage that almost can not get using prepolymer.In addition, if X/Y is less than 3, the big result of molecule quantitative change of prepolymer then, viscosity uprises, and is in the tendency that is difficult to handle curable resin composition.
As the polyvalent alcohol beyond the polycaprolactone polyol more than the trifunctional that contains in the polyhydroxy reactant of the present invention; For example; Can enumerate polycaprolactone glycol, terepthaloyl moietie, 1; 6-pinakon, NSC 6366, TriMethylolPropane(TMP), 1,4-dimethanol hexanaphthene, polycarbonate diol, the hydroxyl that in a molecule, has two above hydroxyls contain vinyl resin, have the polyvalent alcohol of isocyanuric acid ester skeleton.Wherein, because cross-linking density uprises, the hardness of cured article improves, and therefore, is fit to TriMethylolPropane(TMP).These polyvalent alcohols solely use a kind of or make up two or more uses.
In second embodiment, the content of the polycaprolactone polyol that the trifunctional in the polyhydroxy reactant is above is more than the 40 quality % with respect to the total amount of whole polyhydroxy reactants.Thus, the result that the cross-linking density during curing uprises fully, the strength and hardness or the obdurability of cured article uprise fully.From so bring into play the viewpoint of said effect effectively, above-mentioned content is more preferably more than the 50 quality %.Also have, the polyvalent alcohol as raw material when synthesizing above-mentioned prepolymer is under the situation of the polycaprolactone polyol more than the trifunctional, and said polycaprolactone polyol also is equivalent to above-mentioned " polycaprolactone polyol that the trifunctional in the polyhydroxy reactant is above ".
In the first embodiment, the content of the specific ester ring type isocyanic ester in the polymeric polyisocyanate composition is more than the 40 quality % with respect to the total amount of whole polymeric polyisocyanate compositions preferably.Thus, the high-temp resisting high-humidity resisting property of the cured article of curable resin composition is high more fully.From more effectively bringing into play said effect, and, further accelerate the viewpoint of curing speed, above-mentioned content is 40～85 quality % more preferably.Also having, when synthetic above-mentioned prepolymer is that said ester ring type isocyanic ester also is equivalent to above-mentioned " specific ester ring type isocyanic ester " under the situation of specific ester ring type isocyanic ester as the isocyanic ester more than two functional groups of raw material.
Polymeric polyisocyanate composition of the present invention is the composition that is included in the isocyanic ester more than two functional groups that have two above NCOs in the molecule.This polymeric polyisocyanate composition comprises specific ester ring type isocyanic ester and is about to the ester ring type isocyanic ester that chemical structure that NCO is incorporated into secondary carbon(atom) has more than one two functional groups or trifunctional.At this, " secondary carbon(atom) " is meant and two direct bonded carbon atoms of carbon atom.In addition, the ester ring type isocyanic ester of two functional groups or trifunctional is the ester ring type isocyanic ester that in a molecule, has two or three NCOs.
As above-mentioned specific ester ring type isocyanic ester; For example; Can enumerate isophorone diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate) etc. has two functional groups of the chemical structure that on cyclohexane ring, directly combines NCO or the ester ring type isocyanic ester of trifunctional.In addition, also can be for can be with above-mentioned ester ring type isocyanic ester as raw material synthetic isocyanuric acid ester type or biuret type polymeric polyisocyanate.As said polymeric polyisocyanate,, be fit to isocyanuric acid ester type polymeric polyisocyanate from more effectively and reliably playing the viewpoint of effect of the present invention.The polymeric polyisocyanate composition contains specific ester ring type isocyanic ester, compares with the situation that only contains the norbornylene vulcabond ester ring type isocyanic ester such as (NBDI) with such chemical structure thus, and the high-temp resisting high-humidity resisting property of cured article is more superior.
Utilize the synthetic above-mentioned specific ester ring type isocyanic ester of usual method also can, obtain commercially available material and also can.As commercially available ester ring type isocyanic ester, for example, can enumerate trade(brand)name " IPDI ", the identical goods name " H of Di Gesa (デ グ サ ジ ヤ パ Application) Japanese firm's system
12HDI " etc.
Specific ester ring type isocyanic ester uses a kind of separately or makes up two or more uses.
Preferred polymeric polyisocyanate composition contains obtain, the residual prepolymer that NCO is arranged of polycaprolactone polyol reaction through the hydroxyl of the sum that makes isocyanic ester more than two functional groups, lacks with the sum with the NCO that has than this isocyanic ester.This prepolymer is through the reaction of the NCO of the isocyanic ester more than two functional groups and hydroxyl groups, generates urethane bond and obtains.Through containing this prepolymer, the curing speed of curable resin composition becomes faster, and therefore, said compsn is more suitable for liquid transfer mould.In addition, contain prepolymer through said polymeric polyisocyanate composition, the intermiscibility of polyhydroxy reactant and polymeric polyisocyanate composition improves, and the degree of cure shrinkage reduces.In this case, the above isocyanic ester of two functional groups can be specific ester ring type isocyanic ester, also can be the isocyanic ester more than two functional groups in addition.
When synthetic above-mentioned prepolymer, the preferred X/Y of ratio of the sum (Y) of the NCO that the above isocyanic ester of sum (X) and two functional groups of the hydroxyl that has as the polyvalent alcohol of raw material has becomes 0.05～0.3.If X/Y is less than 0.05, then use prepolymer and the above-mentioned effect that plays reduces, be in the tendency of the advantage that almost can not get using prepolymer.In addition, if X/Y is greater than 0.3, the big result of molecule quantitative change of prepolymer then, viscosity uprises, and is in the tendency that is difficult to handle curable resin composition.
As the isocyanic ester more than two functional groups beyond the ester ring type isocyanic ester that contain, specific in the polymeric polyisocyanate composition of the present invention; Fast light, heat-resisting tint permanence is superior; Therefore, be fit to have the above isocyanic ester of two functional groups of alicyclic ring skeleton and/or have the isocyanic ester of isocyanuric acid ester skeleton.Wherein, preferred 1, two (isocyanato methyl) hexanaphthenes of 3-, hexamethylene diisocyanate modification isocyanuric acid ester skeleton contain triisocyanate and/or norbornylene vulcabond.These isocyanic ester use a kind of separately or make up two or more uses.
In the first embodiment, the content of the specific ester ring type isocyanic ester in the polymeric polyisocyanate composition is more than the 40 quality % with respect to the total amount of whole polymeric polyisocyanate compositions.Thus, the high-temp resisting high-humidity resisting property of the cured article of curable resin composition becomes high more fully.From more effectively bringing into play said effect, and, further accelerate the viewpoint of curing speed, more preferably above-mentioned content is 40～85 quality %.Also having, when synthetic above-mentioned prepolymer is that said ester ring type isocyanic ester also is equivalent to above-mentioned " specific ester ring type isocyanic ester " under the situation of specific ester ring type isocyanic ester as the isocyanic ester more than two functional groups of raw material.
In second embodiment, the content of the polycaprolactone polyol that the trifunctional in the polyhydroxy reactant is above is more than the 40 quality % with respect to the total amount of whole polyhydroxy reactants preferably.Thus, the result that the cross-linking density during curing uprises fully, the hardness of cured article or obdurability are high fully.From more effectively bringing into play the viewpoint of said effect, more preferably above-mentioned content is more than the 50 quality %.Also have; When synthetic above-mentioned prepolymer, be that said polycaprolactone polyol also is equivalent to above-mentioned " polycaprolactone polyol more than the trifunctional in the polyhydroxy reactant " under the situation of polycaprolactone polyol above more than the trifunctional as the polyvalent alcohol of raw material.
In the present invention, the polyvalent alcohol that preferably in polyhydroxy reactant, contains is not for to have the non-aromatic compounds of aromatic nucleus at intramolecularly.If polyvalent alcohol has aromatic nucleus, the then coloring resistance property reduction to heat or light of the cured article of curable resin composition, and curing speed exceedingly accelerates, and therefore, is in the tendency that is difficult to be applicable to liquid transfer mould.From identical viewpoint, the isocyanic ester that preferably in the polymeric polyisocyanate composition, contains more preferably contains compound and is non-aromatic compounds for not have the non-aromatic compounds of aromatic nucleus at intramolecularly in two compositions.
The proportioning of polyhydroxy reactant in the curable resin composition of the present invention and the polymeric polyisocyanate composition most preferably NCO that has of the hydroxyl that has of polyhydroxy reactant and polymeric polyisocyanate composition becomes the proportioning of equivalent (equivalent).Thus, mechanical characteristicies such as the optical characteristics such as coloring resistance property to heat or light of cured article, hardness, thermotolerance, wet fastness are more superior.
Except above-mentioned polyhydroxy reactant and the polymeric polyisocyanate composition, containing inhibitor, curing catalysts, releasing agent, hindered amine is that photostabilizer, UV light absorber, inorganic filler, organic filler, coupler, polymerization retarder etc. also can in the curable resin composition of the present invention.In addition, from the viewpoint of the raising of formability, this curable resin composition contains softening agent, static electrification and prevents that agent, fire retardant etc. from also can.These are preferred liquid from the viewpoint of the photopermeability of the cured article of guaranteeing curable resin composition more fully.But, use under the situation of solid matter, be fit to have the particle diameter littler than the light wavelength that should see through.These use a kind of separately or make up two or more uses.
As inhibitor, the viewpoint of especially fast light, heat-resisting tint permanence from improving, the type phenol that is fit to be obstructed is inhibitor.Especially, preferred [2-{3-(the 3-tertiary butyl-hydroxy-5-methyl base phenyl) propionyl group }-1, the 1-dimethyl ethyl]-2; 4,8,10-four oxaspiros [5; 5] it is that sumitomo chemical company system, trade(brand)name " Si Milaite-GA-80 " obtain that undecane, this inhibitor can be used as commercially available article.
Inhibitor in the curable resin composition to contain proportional be 0.05～5 mass parts with respect to total amount 100 mass parts of polyhydroxy reactant and polymeric polyisocyanate composition preferably, more preferably 0.05～0.3 mass parts.If it is proportional less than 0.05 mass parts that this contains, then be in and be difficult to obtain effect as inhibitor, if surpass 5 mass parts, the solvability that then is in to curable resin composition reduces, or the tendency of when the curing of curable resin composition, separating out.
Curable resin composition contains curing catalysts and also can from the viewpoint of the curing speed that obtains being fit to liquid transfer mould.As curing catalysts, the tin such as organo-metallic series catalysts, dibutyl tin lauroleate that can enumerate zirconium system, aluminium system etc. is the phenolate of curing catalysts, DBU, octylate, amine, imidazoles etc.Wherein, since superior to the coloring resistance property of heat, therefore, be fit to the organo-metallic series catalysts.
Curing catalysts in the curable resin composition contain proportional preferably for total amount 100 mass parts of polyhydroxy reactant and polymeric polyisocyanate composition for greater than 0 mass parts and below 1 mass parts, more preferably greater than 0 mass parts and below 0.11 mass parts.If it is proportional greater than 1 mass parts that this contains, then the result that accelerates of curing speed is in the tendency that is difficult to handle curable resin composition.
In addition, curable resin composition is filled in it in die cavity of forming mould and the viewpoint from the release property of forming mould of the cured article after solidifying from improving, and contains releasing agent and also can.As releasing agent, for example, can enumerate polysiloxane series, polyethylene-based, fluorine system, fatty ester is releasing agent.Wherein, owing to show especially good release property, therefore, the preferred fat acid esters is a releasing agent.
Releasing agent in the curable resin composition to contain proportional be 0.05～5 mass parts with respect to total amount 100 mass parts of polyhydroxy reactant and polymeric polyisocyanate composition preferably, more preferably 0.1～2 mass parts.If this contains proportional less than 0.05 mass parts; Then be in and be difficult to bring into play fully tendency as the function of releasing agent; If surpass 5 mass parts; Then be in the tendency that dies down of coloring resistance property to heating of the cured article of curable resin composition, and, the tendency that the solvability of the releasing agent in the curable resin composition reduces be in.
Gelation time under preferred its 165 ℃ of the curable resin composition of the present invention is 10～200 seconds, more preferably 20～180 seconds.Thus, utilize liquid transfer mould to come under the situation of forming and hardening property resin combination, can come moulding well with the molding time identical (mold temperature, molding time) with solid-state transfer mould.Thereby said curable resin composition is useful on its moulding, obtains in the situation of sealing element of photodiode (below, also be labeled as " LED ") packaged piece.If gelation time was less than 10 seconds; Then liquid curable resin composition flows through solidified result before the stream of forming mould fully; In forming mould, can not fill curable resin composition fully, be in the tendency of the cured article (formed body) of the shape that is difficult to obtain to have expectation.In addition, if gelation time surpasses 200 seconds, then be in the tendency that obtains solidifying inadequate formed body easily.
The gelation time of curable resin composition can be through regulating curing catalysts kind or contain containing of proportional, prepolymer proportional, control as polyvalent alcohol, the kind of isocyanic ester, the cooperation ratio of prepolymer in addition.
The curable resin composition of the present invention of above explanation can provide to be exposed to for a long time under the hot and humid environment LED packaged piece that coloring resistance property is also superior fully through its cured article is used with sealing element as LED.In addition, this curable resin composition is fit to liquid transfer mould, therefore, can shorten molding time, boosts productivity.And then the light transmission in the starting stage of the cured article of curable resin composition of the present invention is also good.From these viewpoints, with regard to curable resin composition of the present invention, its cured article is especially useful with sealing element as LED.
(method of manufacture of LED packaged piece)
Secondly, the embodiment that is fit to of the method for manufacture of LED packaged piece of the present invention is described.The method of manufacture of the LED packaged piece of this embodiment has: utilize above-mentioned first curable resin composition of liquid transfer moudling curing molding, obtain the operation of sealing element.Below, structure shown in Figure 1 is specified as an example.
At first, prepare to be liquid curable resin composition under the room temperature of the present invention, it is filled in the jar of shaped device.Therewith differently, prepare the structure that possesses a wiring substrate and be assembled in a plurality of assembling parts of said substrate.This structure possesses: wiring substrate; The adhering part that on the distribution of one of which side, is provided with; The light-emitting diode that on adhering part, forms; Be electrically connected the metal wire of light-emitting diode and the opposing party's distribution.This structure is arranged at the position of the regulation in the die cavity that the forming mould that utilizes shaped device to possess (below, abbreviate " mould " as) forms.Shaped device is used in liquid transfer mould, as long as the shape that the die cavity that utilizes said mould to form is as the purpose cured article does not just limit especially.
Secondly, the starting plunger is pressed into curable resin composition beginning in the jar in the die cavity of mould of the temperature that is heated to be regulation via streams such as runner, pouring gates.Mould generally includes can isolating mold and bed die, forms die cavity through these are linked.Then, through curable resin composition is kept certain hour in die cavity, the curable resin composition that curing molding is filled in die cavity.Thus, the cured article of curable resin composition seals a plurality of assembling parts, and, be adhered to structure.
The temperature of preferred mold is set in above-mentioned stream, the mobile height of curable resin composition, and in die cavity, curable resin composition is the solidified temperature at short notice.This temperature also depends on the composition of curable resin composition, but for example is fit to 120～200 ℃.In addition, the sputtering pressure when preferably being pressed into curable resin composition in the die cavity is set at and can curable resin composition be filled in the pressure in the die cavity integral body very close to each otherly, specifically, and more than the preferred 2MPa.If sputtering pressure less than 2MPa, then is in and is easy to generate not filling part in the die cavity, or in cured article, be easy to generate the tendency in space.
In addition, for the cured article with curable resin composition takes out from mould easily, the coating of mould inner wall face or the injection of releasing agent synform forming cavity also can.And then in order to suppress the generation in the space in the cured article, use can also can to the known vacuum extractor that reduces pressure in the die cavity.
Then, the cured article that structure is reached the curable resin composition bonding with it individually cuts off (cutting) substrate and cured article with a plurality of assembling parts discretely after the die cavity taking-up.Like this, obtain LED packaged piece that the cured article of above-mentioned curable resin composition is possessed as the sealing element of sealing assembling parts.
Method of manufacture according to the LED packaged piece of this embodiment of above explanation can be known, adopts liquid transfer moudling, therefore, can reduce to set set time, thereby improve the productivity of LED packaged piece.In addition, through using the above-mentioned method of forming, obtain to give the effect of shape arbitrarily.
(LED packaged piece)
One example of the LED packaged piece that the method for manufacture of the LED packaged piece through the invention described above shown in Fig. 1 obtains.Fig. 1 is the constructed profile of the LED packaged piece of suitable embodiment of the present invention.The LED packaged piece 10 of this surface installing type (or also be called " chip-shaped ") has: the substrate 1 of insulativity; A pair of wiring layer 2 in the substrate assembling; The adhering part 3 that on a side distribution 2a, is provided with; The light-emitting diode 4 that on adhering part 3, is equipped with; Be electrically connected the metal wire 5 of light-emitting diode 4 and the opposing party's distribution 2b; The sealing element 6 of the part of seal lines layer 2, adhering part 3, light-emitting diode 4 and metal wire 5.
Light-emitting diode 4 so long as order when applying voltage luminous semiconductor element just do not limit especially, can be known light-emitting diode.In addition, metal wire 5 is so long as can be electrically connected light-emitting diode 4 and the conductive metal wires such as metal fine of the opposing party's distribution 2b get final product.
More than in the LED packaged piece 10 of this embodiment of explanation as the sealing element of the parts of the influence that receives temperature or humidity easily; Adopt the cured article of curable resin composition of the present invention; Therefore; Be exposed under the hot and humid environment LED packaged piece that the brightness maintenance is also superior fully for a long time even become.In addition, in the part of its manufacturing process, adopt liquid transfer mould, can shorten molding time thus, boost productivity.And then the perviousness in the starting stage of sealing element is also good, therefore, can keep high brightness for a long time.In addition, through adopting liquid transfer mould, also play the effect that to give lens shape of the taking-up efficient raising of light shown in Figure 1.
More than, suitable embodiment of the present invention has been described, but the present invention is not limited to above-mentioned embodiment.The present invention can carry out various distortion in the scope that does not break away from its aim.
For example, in other embodiments of the method for manufacture of LED packaged piece of the present invention, when forming sealing element,, can adopt casting moulding method or casting though the liquid transfer mould of productivity ratio is poor.In this case, Heating temperature that the curing of curable resin composition is required and heat-up time are depended on the composition of curable resin composition, but preferred 60～150 ℃, 1～10 hour, more preferably 80～150 ℃, 1～10 hour.In addition, in order to reduce to follow the internal stress that solidifies in the cured article that produces, preferably pine for gradually or interimly making temperature to rise and carry out adding.
In addition, as long as the cured article that possesses curable resin composition of the present invention as sealing element in the LED packaged piece just is not limited to above-mentioned embodiment, for example, can be LED packaged piece shown in Figure 2.Surface mounting LED packaged piece 20 shown in the constructed profile of Fig. 2 possesses: light-emitting diode 24; The sealing element with light transmission 26 that is provided with the mode of sealed light emitting diode element 24.Light-emitting diode 24 is disposed at the bottom that utilizes the die cavity portion 28 that box part 27 forms.Light-emitting diode 24 is electrically connected with a side lead frame 22a via adhering part 23, is electrically connected with the opposing party's lead frame 22b via metal wire 25.In this LED packaged piece 20, sealing element 26 forms through the cured article of curable resin composition of the present invention.Also have, having an even surface of sealing element 26 do not have the light accumulative function of sending from light-emitting diode 24.
Couple of conductor frame 22 is embedded in box part 27 and assembles.Couple of conductor frame 22, adhering part 23, light-emitting diode 24 and metal wire 25 be respectively with above-mentioned embodiment in wiring layer 2, adhering part 3, light-emitting diode 4 and metal wire 5 identical materials get final product.In addition, box part 27 has the shape that can curable resin composition be remained in die cavity portion 28, and the opening portion of die cavity portion 28 forms circle.
And then LED packaged piece of the present invention is not limited to surface installing type, can be the housing type.
(second curable resin composition)
Secondly, second curable resin composition of the present invention is described.Second curable resin composition of the present invention contains: polyhydroxy reactant; The polymeric polyisocyanate composition; It contains the chemical structure that NCO is incorporated into secondary carbon(atom) and has the isocyanuric acid ester type isocyanic ester more than more than one two functional groups; The second-order transition temperature of the cured article of said curable resin composition is more than 110 ℃, and the thermal expansivity when second-order transition temperature is following is 10.0 * 10
-5/ ℃ below, the thermal expansivity when second-order transition temperature is above is 20.0 * 10
-5/ ℃ below, and the bending elastic modulus under 25 ℃ is more than the 1500MPa.
Also have, first and second curable resin composition of the present invention is through making the reaction of A liquid that contains polyhydroxy reactant and the B liquid that contains the polymeric polyisocyanate composition, obtaining " resin combination of biliquid type " of cured article.
The broken string of the metal wire in the temperature cycling test of photosemiconductor or peel off the curing rerum natura of the resin that depends on sealing element; Bending elastic modulus under 25 ℃ of cured article is under the situation of the above hard of 1000MPa; The stress demulcent effect of resin self reduces; Therefore, preferred thermal expansivity is as far as possible little, and second-order transition temperature is more than the upper limit of test temperature scope.
Through the curable resin composition among the present invention is solidified, obtain utilizing the reaction of hydroxyl groups and NCO to form the cured article of three-dimensional crosslinking structure.Curing rerum naturas such as the second-order transition temperature of cured article, thermal expansivity, bending elastic modulus depend on the kind of polyvalent alcohol or isocyanic ester, those use level etc.; But, can realize the reducing of high temperatureization, thermal expansivity of second-order transition temperature especially through use isocyanuric acid ester type isocyanic ester as the polymeric polyisocyanate composition.
In addition; Use secondary carbon(atom) bonded chemical structure to have the isocyanuric acid ester type isocyanic ester more than more than one two functional groups as the polymeric polyisocyanate composition with NCO and alicyclic ring skeleton; Compare with primary carbon atom bonded isocyanic ester with NCO thus; For example be used under the situation of sealing of LED, can suppress the reduction of the brightness in the continuity point lantern test under the hot and humid condition.
Equally; As polyhydroxy reactant; Using weight-average molecular weight is below 500; And hydroxyl value be the above polycaprolactone polyol of the above trifunctional of 300mgKOH/g, and weight-average molecular weight be below 350, and hydroxyl value is the above aliphatic polyol of the above trifunctional of 500mgKOH/g, can realize the reducing of high temperatureization, thermal expansivity of second-order transition temperature.
In addition; As polyhydroxy reactant, preferred use to contain make polyvalent alcohol and have that isocyanate reaction more than two functional groups of NCO of the sum that the sum of the hydroxyl that has than this polyvalent alcohol lacks obtains, the residual polyhydroxy reactant P that the prepolymer of hydroxyl is arranged
ALiquid.And then; As the polymeric polyisocyanate composition, preferred obtain, the residual polymeric polyisocyanate P that the prepolymer of NCO is arranged of polyol reaction that uses the hydroxyl that contains the sum that the sum that makes the above isocyanic ester of two functional groups and have the NCO that has than this isocyanic ester lacks
BLiquid.Also have, preferably through making above-mentioned P
BThe residual NCO of liquid, with contain the above-mentioned P of the hydroxyl of equivalent
ACured article is made in the liquid reaction.Also have, in following explanation, for above-mentioned P
ALiquid and above-mentioned P
BLiquid is called " A liquid " with the polyhydroxy reactant that does not contain above-mentioned prepolymer, and the polymeric polyisocyanate composition that does not contain above-mentioned prepolymer is called " B liquid ".
Use these P
ALiquid and P
BLiquid under the situation of preparing resin compsn, is compared with the situation of making cured article through the monomer of polyhydroxy reactant and polymeric polyisocyanate composition, and it is little to have so-called cure shrinkage, also has the superior strong point of consistency, therefore preferred.And then curing speed is fast, therefore, can be used in fast curing-formed operations such as liquid transfer mould.
In addition, making P
BUnder the situation of liquid, as polyvalent alcohol, preferably using weight-average molecular weight is below 350, and hydroxyl value is the above aliphatic polyol of the above trifunctional of 500mgKOH/g.This be because: make the reaction earlier of the slow composition of speed of response in polyhydroxy reactant and the polymeric polyisocyanate composition, form prepolymer, advantageously act on above-mentioned consistency, rapidly-curable thus.
Preferred above-mentioned P
BPrepolymer in the liquid is that to make the ratio (X/Y) of above-mentioned polyvalent alcohol and above-mentioned isocyanic ester hydroxyl equivalent X and the NCO equivalent Y in the above-mentioned isocyanic ester in polyvalent alcohol be to react under 0.05～0.30 the condition to obtain.If above-mentionedly surpass 0.30 than (X/Y), then the molecule quantitative change of prepolymer is big, and viscosity is high, causes reluctant problem, if than (X/Y) less than 0.05, then almost can not get the effect of pre-polymerization materialization.In addition, the synthetic of prepolymer can shorten through adding catalyzer, but for fear of painted, preferably under catalyst-free with room temperature or reacting by heating.
Equally, preferred above-mentioned P
APrepolymer in the liquid is to be that reaction obtains under the condition more than 3 through the ratio (X/Y) that makes above-mentioned polyvalent alcohol and above-mentioned isocyanic ester hydroxyl equivalent X and the NCO equivalent Y in the above-mentioned isocyanic ester in above-mentioned polyvalent alcohol.If above-mentioned than (X/Y) less than 3, then almost can not get the effect of pre-polymerization materialization.
As what use in the present invention NCO and secondary carbon(atom) bonded chemical structure had the isocyanuric acid ester type isocyanic ester more than more than one two functional groups; Especially preferred isophorone diisocyanate (3-isocyanic ester methyl-3; 5,5-3-methyl cyclohexanol based isocyanate) trimer, in addition; Can be 1, the trimer of two (isocyanato methyl) hexanaphthenes of 3-.Form triple polyisocyanate annulus with primary carbon bonded NCO in the Trimerization of Isophorone Diisocyanate thing, three residual NCOs combine with the secondary carbon(atom) of alicyclic ring skeleton.
In addition, as other isocyanic ester in the polycaprolactone polyol, preferably has the isocyanic ester of ester ring type skeleton; Can enumerate 1; Two (isocyanato methyl) hexanaphthenes of 3-, norbornylene vulcabond (2, the two isocyanato methyl [2 of 5-(2,6); 2,1] heptane), isophorone diisocyanate, 4-4 ' methylene-bis (cyclohexyl isocyanate), isopropylidene two (4-cyclohexyl isocyanate), cyclohexyl diisocyanate etc.Wherein, especially preferred 1, two (isocyanato methyl) hexanaphthenes of 3-, norbornylene vulcabond (2, the two isocyanato methyl of 5-(2,6) [2,2,1] heptane).In addition, mixing the multiple ester ring type isocyanic ester vulcabond of use also can.
In addition, ratio in the polymeric polyisocyanate composition, that NCO and secondary carbon(atom) bonded chemical structure are had an isocyanuric acid ester type isocyanic ester more than more than one two functional groups is that benchmark is more than the 40 quality % with the solids component total amount in the polymeric polyisocyanate composition preferably.If the ratio of isocyanuric acid ester type isocyanic ester then is in the tendency that is difficult to obtain the second-order transition temperature more than 110 ℃ less than 40 quality %.
As in the polyhydroxy reactant that uses among the present invention, weight-average molecular weight is below 350, and hydroxyl value is the above aliphatic polyol of the above trifunctional of 500mgKOH/g, preferred TriMethylolPropane(TMP), propane-1,2,3-triol.In addition, use the verivate of those aliphatic polyols also can.As the aliphatic polyol verivate, preferred addition the verivate of oxyethane or propylene oxide.But, also depend on the use level of aliphatic polyol verivate, but, expect that its weight-average molecular weight is below 350 for cured article obtains the second-order transition temperature more than 110 ℃.
Cooperation ratio as each composition in the polyhydroxy reactant; Be benchmark preferably with the solids component total amount in the polyhydroxy reactant; Weight-average molecular weight is below 500, and hydroxyl value is that the above polycaprolactone polyol of the above trifunctional of 300mgKOH/g is more than the 40 quality %, in addition; Weight-average molecular weight is below 350, and hydroxyl value is that the above aliphatic polyol of the above trifunctional of 500mgKOH/g is after the 30 quality %.If the cooperation ratio of above-mentioned each composition then is in the tendency that cured article is difficult to obtain the second-order transition temperature more than 110 ℃ less than above-mentioned lower value.
In addition, as other polyvalent alcohol kinds in the polyhydroxy reactant, preferred caprolactone diol, carbonic ether glycol, polyester glycol, polyether glycol, and 1,4-butyleneglycol and 1, aliphatic diols such as ammediol etc.
And then, in curable resin composition of the present invention, contain the type phenol of being obstructed and be inhibitor also can, be included in above-mentioned A liquid, B liquid, P
ALiquid and P
BAny of liquid also can.From deliquescent viewpoint, preferably be contained in the liquid that contains big quantity gathers isocyanate composition.Using the type phenol that is obstructed through combination is inhibitor, can significantly improve photostabilization, thermotolerance, the mechanical characteristics of curable resin composition.
As the above-mentioned type phenol that is obstructed is inhibitor, for example, can enumerate 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; The 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5; 5] undecane, phenylpropionic acid, 3, two (1, the 1-the dimethyl ethyl)-4-hydroxyls of 5-, C7-C9 side chain alkyl ester, 4; 4 '-butylidene two (the 6-tertiary butyl-3-methylphenol), 2,6 di tert butyl 4 methyl phenols, 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol) etc.Wherein, especially preferred 3,9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1,1-dimethyl ethyl]-2; 4,8,10-four oxaspiros [5; 5] undecane or phenylpropionic acid, 3, two (1, the 1-the dimethyl ethyl)-4-hydroxyls of 5-, C7-C9 side chain alkyl ester.
The addition of above-mentioned inhibitor is that benchmark is 0.05～5 quality % with the solids component total amount of curable resin composition preferably, more preferably 0.05～0.3 quality %.Can not obtain tendency fully if the addition of inhibitor less than 0.05 quality %, then is in, on the other hand,, then be in the tendency that the problem of separating out when deliquescent problem taking place promptly solidifying etc. takes place if surpass 5 quality % as the effect of inhibitor.
In addition, usually, the reactivity of hydroxyl and ester ring type NCO is reactive slower than hydroxyl and aromatic isocyanate, therefore, through adding curing catalysts, can shorten set time.
As this catalyzer, do not limit especially, but for example, can enumerate the phenolate, octylate, amine, imidazoles of organo-metallic catalyst, dibutyl tin lauroleate, the DBU of zirconium or aluminium etc.Wherein, from the aspect of tint permanence, especially preferred organo-metallic series catalysts, for example, the secondary butyrates of aluminium, ethyl acetoacetic ester aluminium diisopropyl hydrochlorate, zirconium three butoxy Acetyl Acetone salt, the tetra-acetylated acetone salt of zirconium etc.
The addition of above-mentioned catalyzer is that benchmark is below the 1 quality % with the solids component total amount of curable resin composition preferably, below the especially preferred 0.1 quality %.If the addition of catalyzer surpasses 1 quality %, then curing speed becomes too fast, is in the tendency that is difficult to handle curable resin composition.In addition, it is many more to be in addition, more the tendency of easy colorizing.
In curable resin composition of the present invention, except mentioned component, can also add hindered amine and be photostabilizer or phosphorous antioxidant, UV light absorber, inorganic filler, organic filler, coupler, polymerization retarder etc.In addition, from the viewpoint of formability, add releasing agent, softening agent, static electrification and prevent that agent, fire retardant etc. from also can.These are preferred liquid from the viewpoint of the photopermeability of guaranteeing curable resin composition more fully, but use under the situation of solid matter, and expectation has the particle diameter below the wavelength of use.
As releasing agent, can add fatty ester system, polysiloxane series, polyethylene-based, fluorine is a releasing agent.Wherein, especially the preferred fat acid esters is a releasing agent.The addition of releasing agent is 0.05～5 mass parts with respect to solids component total amount 100 mass parts of the mixture of polyhydroxy reactant and isocyanate prepolymer composition preferably, more preferably 0.1～2 mass parts.Be difficult to obtain fully tendency if addition less than 0.05 mass parts, then is in, on the other hand,, then be in the tendency of the problem that takes place on painted or the solvability if surpass 5 mass parts as the effect of releasing agent.
Gelation time under preferred 165 ℃ of the curable resin composition of the present invention is 10～200 seconds.Be made as this scope through a gelation time, can with the roughly the same condition of molding of solid-state transfer mould in the past under, carry out making based on the resin-sealed or optics of the optical semiconductor of liquid transfer mould.If solidify before gelation time less than 10 seconds, then flows through in the stream of curable resin composition solution in forming mould fully, be in forming composition and be easy to generate the tendency of not filling position or space.On the other hand, if gelation time surpasses 200 seconds, then having becomes the tendency of solidifying inadequate forming composition.
In curable resin composition of the present invention, polyhydroxy reactant (above-mentioned A liquid and/or above-mentioned P
ALiquid) and polymeric polyisocyanate composition (above-mentioned B liquid and/or above-mentioned P
BLiquid) hydroxyl equivalent in the proportioning preferred polyol composition and the ratio of the NCO equivalent in the polymeric polyisocyanate composition (hydroxyl equivalent/NCO equivalent) become 0.7～1.3 proportioning, more preferably become 0.8～1.1 proportioning.If the tendency that this thermotolerance, optical characteristics, mechanical characteristics that, then has cured article than departing from 0.7～1.3 reduces.
(photosemiconductor)
As the method for manufacture of the cured article that has used curable resin composition of the present invention (optics etc.), do not limit especially, but for example, can enumerate polyol blend composition (above-mentioned A liquid and/or above-mentioned P
ALiquid) and polymeric polyisocyanate composition (above-mentioned B liquid and/or above-mentioned P
BLiquid), curable resin composition solution evenly after, cast, pour into a mould or make it flow into mould, be heating and curing, obtain the method for cured article etc. thus.Also have, utilize liquid transfer mould to come, preferred A liquid and P with under the short period of time solidified situation
BThe combination of liquid.
The stirring means of these biliquids can be enumerated the method based on rotation stirring or ultrasonic dispersing etc., need its stirring be become even for curable resin composition.In addition, also can be after having mixed curable resin composition, freezing preservation forms a liquid-type curable resin composition solution.In this case, can before casting, cast, at room temperature thaw and use.
In addition, with resin compound casting, pour into a mould or make before it flows into mould, for the carbonic acid gas of removing the bubble of when mixing, sneaking into or being generated by the reaction of isocyanic ester and airborne moisture, expectation is with the resin compound vacuum defoamation.
Utilize heating condition under teeming practice, the casting solidified situation to depend on kind, the combination of each composition, but under preferred 60～150 ℃, about 1～10 hour, more preferably under 80～150 ℃, about 1～5 hour.In addition, for the internal stress that reduces to be taken place by rapid curing reaction, expectation heats up solidification value interimly.
In addition, photosemiconductor of the present invention possesses the parts (optics, sealing element etc.) that come moulding to obtain the liquid transfer moudling of the curable resin composition utilization of the invention described above.Using liquid transfer mould; Under the situation of the resin-sealed or optics of making optical semiconductor, for example, can be through curable resin composition of the present invention be injected in the jar of shaped device; The operation plunger; Curable resin composition in the jar is transferred to the die cavity portion that formed by mold and bed die, then, curable resin composition is heating and curing carries out.Die temperature expectation curable resin composition can move in the mould stream, and can be with short period of time solidified temperature in die cavity, preferred about 120 ℃～200 ℃.
In addition, the sputtering pressure of curable resin composition does not limit so long as do not take place in the resin combination in die cavity not fill and do not put or the pressure of the scope in space gets final product especially, but more than the preferred 2MPa.If less than 2MPa, then having, sputtering pressure is easy to generate the not tendency of filling part.
In addition, also can apply, spray releasing agent in die side in order to improve release property.And then, also can use the device that vacuumizes in order to suppress the generation in space.The device that can vacuumize does not limit especially, can use known device.In addition, under the situation of liquid transfer mould, also expectation as required, carry out moulding after, carry out after fixing.
More than the optical transparence of the cured article of the curable resin composition of the present invention of explanation is high, is suitable as fast light, heat-resisting optical characteristics such as painted, mechanical characteristics sealing resins superior, optical semiconductor purposes such as light emission diode package member (LED), phototransistor, photodiode, solid-state imager.In addition, the curable resin composition of the application of the invention can utilize liquid transfer mould to come efficient to carry out the resin-sealed of optical semiconductor well, can productivity make photosemiconductors such as LED well.
Embodiment
Below, through embodiment, illustrate in greater detail the present invention, but the present invention is not limited to these embodiment.
(embodiment 1)
Mixing as polyhydroxy reactant, weight-average molecular weight: 300 and polycaprolactonetriol A1 (wearing West Road chemical industrial company system, trade(brand)name " pula Ke Xier 303 ") 28.3 mass parts and the weight-average molecular weight of hydroxyl value: 540mgKOH/g: 500 and polycarbonate diol A2 (wearing West Road chemical industrial company system, trade(brand)name " pula Ke Xier CD205PL ") 28.3 mass parts of hydroxyl value: 230mgKOH/g and as the polymeric polyisocyanate composition, isophorone diisocyanate B1 (Di Gesa Japanese firm system, trade(brand)name " IPDI ") 43.3 mass parts and as the type phenol that is obstructed be inhibitor [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; The 1-dimethyl ethyl]-2; 4; 8; 10-four oxaspiros [5; 5] undecane C1 (sumitomo chemical company system, trade(brand)name " Si Milaite GA-80 ") 0.1 mass parts; Will be as described above after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve, vacuum deaerator has obtained the solution S 1 of curable resin composition.
In addition, prepare the assembling parts of the sealing element that does not possess the LED packaged piece shown in Figure 2 with being described below.Embed the diameter that moulding formed the opening portion of die cavity portion in lead frame utilization and be the box part that the gathers phthalimide system (physical dimension: width 3.2mm * depth 2.6mm * thickness 1.8mm) of 2.4mm with shape identical with structure shown in Figure 2.Secondly, on the lead frame that exposes to the bottom of die cavity portion, light-emitting diode (emission wavelength: 470nm) has been installed via silver-colored paste.Secondly, use gold thread, utilize wire bonding, connect the terminal and the light-emitting diode of the lead frame of the side that light-emitting diode is not installed, obtained assembling parts.
Secondly, make in the die cavity portion that the solution S 1 of above-mentioned curable resin composition flows in the above-mentioned assembling parts and filling.Secondly, for the solution S 1 of the curable resin composition of filling, with 80 ℃ following 1 hour, 100 ℃ following 1 hour, 120 ℃ following 1 hour, and 150 ℃ of following conditions of 3 hours implement to be heating and curing processing, obtained cured article as sealing element.Like this, accomplished the LED packaged piece.
(embodiment 2)
Mixing is as the above-mentioned polycarbonate diol A2 of the above-mentioned polycaprolactonetriol A1 of 35.0 mass parts of polyhydroxy reactant, 7.0 mass parts, as 4 of 28.7 mass parts of polymeric polyisocyanate composition, 4 '-methylene-bis (cyclohexyl isocyanate) B2 (Di Gesa Japanese firm system, trade(brand)name " H
12MDI "), the isocyanuric acid ester type triisocyanate B3 (Asahi Chemical Industry's pharmaceutical chemicals corporate system, trade(brand)name " Du Laite THA-100 ") of 29.4 mass parts, and the conduct of 0.1 mass parts be obstructed type phenol be inhibitor above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; the 1-dimethyl ethyl]-2; 4,8,10-four oxaspiros [5; 5] undecane C1; after will the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve as described above, vacuum deaerator has obtained the solution S 2 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 2 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
(embodiment 3)
Mixing is as the above-mentioned polycaprolactonetriol A1 of 40.9 mass parts of polyhydroxy reactant, 4.5 mass parts TriMethylolPropane(TMP) A3 (Perstorp corporate system), as above-mentioned 4 of 25.8 mass parts of polymeric polyisocyanate composition; 1 of 4 '-methylene-bis (cyclohexyl isocyanate) B2,29.7 mass parts; Two (isocyanic ester methyl) the hexanaphthene B4 (Mitsui Chemicals urethane corporate system, trade(brand)name " Plutarch nanotesla T600 ") of 3-, and the conduct of the 0.1 mass parts type phenol that is obstructed be above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1,1-dimethyl ethyl]-2,4 of inhibitor; 8; 10-four oxaspiros [5,5] undecane C1 is after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve as described above; Vacuum deaerator has obtained the solution S 3 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 3 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
(embodiment 4)
At first, mix the above-mentioned 4 of above-mentioned TriMethylolPropane(TMP) A3 as 2.8 mass parts of polyhydroxy reactant, 27.6 mass parts, behind 4 '-methylene-bis (cyclohexyl isocyanate) B2, under 100 ℃, said mixture was stirred 3 hours, obtained prepolymer P1 thus.
Mix the above-mentioned prepolymer P1 of 30.4 mass parts, as the TriMethylolPropane(TMP) A3 of the above-mentioned polycaprolactonetriol A1 of 21.7 mass parts of polyhydroxy reactant, 11.7 mass parts, as above-mentioned 1 of the above-mentioned isocyanuric acid ester type triisocyanate B3 of 10.7 mass parts of polymeric polyisocyanate composition, 25.6 mass parts; Two (isocyanic ester methyl) the hexanaphthene B4 of 3-, and the conduct of 0.1 mass parts be obstructed type phenol be inhibitor above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; The 1-dimethyl ethyl]-2; 4,8,10-four oxaspiros [5; 5] undecane C1; Will be as described above after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve, vacuum deaerator has obtained the solution S 4 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 4 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
(embodiment 5)
Mixing is as the above-mentioned polycarbonate diol A2 of the above-mentioned polycaprolactonetriol A1 of 23.3 mass parts of polyhydroxy reactant, 23.3 mass parts, as above-mentioned (4 of 20.9 mass parts of polymeric polyisocyanate composition; The above-mentioned isocyanuric acid ester type triisocyanate B3 of 4 '-methylene-bis (cyclohexyl isocyanate) B2,32.1 mass parts, and the conduct of 0.1 mass parts be obstructed type phenol be inhibitor above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; The 1-dimethyl ethyl]-2; 4,8,10-four oxaspiros [5; 5] ten-alkane C1; Will be as described above after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve, vacuum deaerator has obtained the solution S 5 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 5 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
(embodiment 6)
Mixing is as the weight-average molecular weight of 29.9 mass parts of polyhydroxy reactant: the above-mentioned polycarbonate diol A2 of the polycaprolactonetriol A4 of 500, hydroxyl value: 310mgKOH/g (wearing West Road chemical industrial company system, trade(brand)name " pula Ke Xier 305 "), 29.0 mass parts, as above-mentioned 4 of 29.6 mass parts of polymeric polyisocyanate composition; The above-mentioned isocyanuric acid ester type triisocyanate B3 of 4 '-methylene-bis (cyclohexyl isocyanate) B2,11.4 mass parts, and the conduct of 0.1 mass parts be obstructed type phenol be inhibitor above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; The 1-dimethyl ethyl]-2; 4; 8; 10-four oxaspiros [5,5] undecane C1 is after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve as described above; Vacuum deaerator has obtained the solution S 6 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 6 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
(comparative example 1)
Mixing as above-mentioned polycarbonate diol A2 30.1 mass parts of polyhydroxy reactant, polycaprolactonetriol A1,6.0 mass parts, as the above-mentioned isocyanuric acid ester type triisocyanate B3 of 63.4 mass parts of polymeric polyisocyanate composition, and the conduct of 0.1 mass parts be obstructed type phenol be inhibitor above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; The 1-dimethyl ethyl]-2; 4,8,10-four oxaspiros [5; 5] undecane C1; Will be as described above after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve, vacuum deaerator has obtained the solution S 6 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 6 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
(comparative example 2)
Mixing is as the above-mentioned polycaprolactonetriol A1 of 51.8 mass parts of polyhydroxy reactant, as above-mentioned 1 of 48.2 mass parts of polymeric polyisocyanate composition; Two (isocyanic ester methyl) the hexanaphthene B4 of 3-, and the conduct of the 0.1 mass parts type phenol that is obstructed be above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1,1-dimethyl ethyl]-2,4 of inhibitor; 8; 10-four oxaspiros [5,5] undecane C1 is after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve as described above; Vacuum deaerator has obtained the solution S 7 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 7 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
(comparative example 3)
Mixing as the above-mentioned polycaprolactonetriol A1 of 50.3 mass parts of polyhydroxy reactant, as the norbornylene diisocyanate B 5 (the military field of Mitsui pharmaceutical chemicals corporate system, trade(brand)name " the special NBDI of gram Spasmonal ") of 49.7 mass parts of polymeric polyisocyanate composition, and the conduct of 0.1 mass parts be obstructed type phenol be inhibitor above-mentioned [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1; The 1-dimethyl ethyl]-2; 4,8,10-four oxaspiros [5; 5] undecane C1; Will be as described above after the blended mixture utilizes ultrasonic dispersing to disperse equably, dissolve, vacuum deaerator has obtained the solution S 8 of curable resin composition.
Secondly, replace the solution S 1 of curable resin composition, use the solution S 8 of this curable resin composition, in addition,, accomplished the LED packaged piece with embodiment 1 identical ground.
The composition of summing up the curable resin composition in above-mentioned each embodiment, the comparative example is illustrated in the table 1.
[table 1]
[hot and humid some lantern test]
Make the electric current of DC20mA flow through the LED packaged piece that obtains, LED is lit a lamp.Use moment multichannel light measurer ianthone Da mound electronics corporation system), measure brightness L1 at this moment.Secondly, the LED packaged piece is disposed in 85 ℃, the constant temperature and humidity cabinet of 85%RH, makes the electric current of DC20mA flow through said LED packaged piece, lighted under the state of LED, kept 1000 hours.Then, the LED packaged piece is taken out from constant temperature and humidity cabinet, the electric current of DC20mA is flow through, light LED, measured brightness L2.The ratio (L2/L1) of the brightness in the constant temperature and humidity cabinet configuration front and back is made as " brightness sustainment rate "; With this brightness sustainment rate is that average evaluation more than 0.8 is " A "; With being " B " more than 0.7 and less than 0.8 average evaluation, will less than 0.7 average evaluation " C ".The result is illustrated in the table 2.
[table 2]
[mensuration of gelation time]
The curable resin composition 0.2g that obtains as described above carried put, use gelation trier (SYSTEM SEKKO corporate system), utilize the semicure method to measure gelation time being heated to be on 165 ℃ the hot plate.The result is illustrated in the table 2.
[liquid transfer mould property test]
The solution of the curable resin composition that obtains as described above is filled in the jar of transfer mould with shaped device.Secondly, the operation plunger is pressed into curable resin composition in the die cavity of the mould that is heated to be 165～175 ℃ via stream in jar.Sputtering pressure is 4～15MPa, and the time that is pressed into of the curable resin composition in die cavity is 20～50 seconds.Secondly, curable resin composition was remained in the die cavity 180～300 seconds.Also have, with regard to Heating temperature, the sputtering pressure of mould, be pressed into time, hold-time, according to resin or the mold shape used; Differences such as the entering easness in the temperature dependency of curing speed or space, filling easness; Therefore, according to resin, suitably impose a condition.The LED packaged piece shown in Figure 1 of the physical dimension 5.1mm * 3.9mm * 4.7mm that obtains like this with microscopic examination.Do not confirm to the space in appearance and be not evaluated as " A " under the situation of filling part at it, with confirming to the space or not being evaluated as " C " under any situation of filling part.The result is illustrated in the table 2.
The LED packaged piece of embodiment 5 becomes " B " in hot and humid some lantern test be that 4 '-methylene-bis (cyclohexyl isocyanate) is than lacking among the embodiment 2 because of 4 in the curable resin composition.
(embodiment 7)
In weight-average molecular weight: among the polycaprolactonetriol A1 of 300, hydroxyl value: 540mgKOH/g (wearing the trade(brand)name " pula Ke Xier 303 " of West Road chemical company system) as 7.8 mass parts of polyhydroxy reactant; Add TriMethylolPropane(TMP) A3 (Perstorp corporate system), and the weight-average molecular weight of 1.5 mass parts: the polycarbonate diol A2 of 500, hydroxyl value: 230mgKOH/g (wearing the trade(brand)name " pula Ke Xier CD205PL " of West Road chemical company system) of 5.0 mass parts; Carry out heated and stirred, obtained uniform polyhydroxy reactant A liquid.
On the other hand; Above-mentioned (A3) 0.56 mass parts is made an addition to 4; In 4 '-methylene-bis (cyclohexyl isocyanate) B6 (firmly changing Bayer urethane Co., Ltd. system, trade(brand)name " Di Simo joule W "), 8.0 mass parts; Under nitrogen atmosphere, reacted 1 hour down at 100 ℃, make the residual prepolymer of NCO.
In addition; As the polymeric polyisocyanate composition; Mix above-mentioned prepolymer 8.56 mass parts, norbornylene diisocyanate B 5 (the military field of Mitsui pharmaceutical chemicals corporate system, trade(brand)name " the special NBDI of gram Spasmonal ") 8.4 mass parts, as N-BUTYL ACETATE solution B 7 (Degussa corporate system, trade(brand)name " VESTANATT1890 ") 21.7 mass parts of the isocyanuric acid ester type isocyanic ester 70 quality % of Trimerization of Isophorone Diisocyanate thing, and the conduct of the 0.05 mass parts type phenol that is obstructed be 3 of inhibitor, 9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1,1-dimethyl ethyl]-2; 4; 8, behind 10-four oxaspiros [5,5] the undecane C1 (sumitomo chemical company system, trade(brand)name " Si Milaite GA-80 "); Under reduced pressure add the heat extraction N-BUTYL ACETATE, obtained polymeric polyisocyanate composition P
BLiquid.
Mix above-mentioned A liquid 14.3 mass parts and above-mentioned P
BLiquid 32.2 mass parts (ratio=1.0 of hydroxyl equivalent/NCO equivalent) have obtained curable resin composition solution.After the curable resin composition solution decompression deaeration that obtains; Make in the mould of its spacer that has flowed into the sheet glass double team the thick silicone system of 3mm; Be heating and curing in following 2 hours with 80 ℃ following 1 hour, 100 ℃ following 1 hour, 150 ℃, made the thick cured article of 3mm.
In addition; With the die cavity portion casting of the curable resin composition solution behind the vacuum deaerator to the polyphtalamide control surface mount type LED of the physical dimension 3.2mm that the LED element is installed * 2.6mm * 1.8mm, die cavity internal diameter 2.4mm (
); Be heating and curing in following 2 hours with 80 ℃ following 1 hour, 100 ℃ following 1 hour, 150 ℃, made the surface mounting LED packaged piece.
(embodiment 8)
As polyhydroxy reactant, in above-mentioned (A1) 5.7 mass parts, add above-mentioned (A3) 5.9 mass parts and above-mentioned (A2) 1.5 mass parts, carry out heated and stirred, form uniform polyhydroxy reactant A liquid.
On the other hand, above-mentioned (A3) 0.65 mass parts is made an addition to above-mentioned (B6) 8.0 mass parts, under nitrogen atmosphere, reacted 1 hour down, made the residual prepolymer of NCO at 100 ℃.
In addition, as the polymeric polyisocyanate composition, mix above-mentioned prepolymer 8.65 mass parts, above-mentioned (B5) 8.4 mass parts, above-mentioned (B7) 21.7 mass parts and above-mentioned (C1) 0.05 mass parts after, under reduced pressure add the heat extraction N-BUTYL ACETATE, made polymeric polyisocyanate composition P
BLiquid.
Mix above-mentioned A liquid 13.1 mass parts and above-mentioned P
BLiquid 32.3 mass parts (ratio=1.0 of hydroxyl equivalent/NCO equivalent) behind the vacuum deaerator, with embodiment 7 identical ground, are made thick cured article and the surface mounting LED packaged piece of 3mm.
(embodiment 9)
As polyhydroxy reactant, in above-mentioned (A1) 32.3 mass parts, add above-mentioned (A3) 32.9 mass parts and above-mentioned (A2) 8.4 mass parts, carry out heated and stirred, form uniform polyhydroxy reactant A liquid.
On the other hand, above-mentioned (A3) 3.6 mass parts are made an addition to above-mentioned (B6) 30.0 mass parts, under nitrogen atmosphere, reacted 1 hour down, made the residual prepolymer of NCO at 100 ℃.
In addition; As the polymeric polyisocyanate composition; After mixing the isocyanuric acid ester type polymeric polyisocyanate B8 (firmly changing company of Bayer urethane Co., Ltd., trade(brand)name " this close joule of N3300 ") and above-mentioned (C1) 0.29 mass parts of the hexamethylene diisocyanate of above-mentioned prepolymer 33.6 mass parts, above-mentioned (B5) 53.1 mass parts, above-mentioned (B7) 122.3 mass parts, 11.0 mass parts; Under reduced pressure add the heat extraction N-BUTYL ACETATE, made polymeric polyisocyanate composition P
BLiquid.
Mix above-mentioned A liquid 73.5 mass parts and above-mentioned P
BLiquid 220.3 mass parts (ratio=1.0 of hydroxyl equivalent/NCO equivalent) behind the vacuum deaerator, with embodiment 7 identical ground, are made thick cured article and the surface mounting LED packaged piece of 3mm.
(embodiment 10)
As polyhydroxy reactant, in above-mentioned (A1) 12.1 mass parts, add above-mentioned (A3) 12.3 mass parts, carry out heated and stirred, form uniform polyhydroxy reactant A liquid.
In addition; As the polymeric polyisocyanate composition; Mix above-mentioned (B5) 8.0 mass parts, 1; After two (isocyanic ester methyl) hexanaphthene B4 (Mitsui Chemical Polyurethane Co., Ltd's system, trade(brand)name " Plutarch nanotesla T600 ") 15.0 mass parts of 3-, above-mentioned (B7) 55.1 mass parts and above-mentioned (C1) 0.10 mass parts, under reduced pressure add the heat extraction N-BUTYL ACETATE, made polymeric polyisocyanate composition B liquid.
Mix above-mentioned A liquid 24.4 mass parts and above-mentioned B liquid 61.7 mass parts (ratio=1.0 of hydroxyl equivalent/NCO equivalent), behind the vacuum deaerator,, make thick cured article and the surface mounting LED packaged piece of 3mm with embodiment 7 identical ground.
(comparative example 4)
Mixing is as above-mentioned (A1) 15.2 mass parts of polyhydroxy reactant A liquid with as above-mentioned (B5) 15.0 mass parts and above-mentioned (C1) 0.03 mass parts (hydroxyl equivalent/NCO equivalent=1.0) of polymeric polyisocyanate composition B liquid; Behind the vacuum deaerator; With embodiment 7 identical ground, make thick cured article and the surface mounting LED packaged piece of 3mm.
(comparative example 5)
As polyhydroxy reactant, in above-mentioned (A1) 6.5 mass parts, add above-mentioned (A3) 4.1 mass parts and above-mentioned (A2) 1.2 mass parts, carry out heated and stirred, form uniform polyhydroxy reactant A liquid.
On the other hand, above-mentioned (A3) 0.46 mass parts is made an addition to above-mentioned (B6) 10.0 mass parts, under nitrogen atmosphere, reacted 1 hour down, made the residual prepolymer of NCO at 100 ℃.
In addition, as the polymeric polyisocyanate composition, mix above-mentioned prepolymer 10.46 mass parts, above-mentioned (B5) 9.6 mass parts and above-mentioned (C1) 0.03 mass parts after, under reduced pressure add the heat extraction N-BUTYL ACETATE, made polymeric polyisocyanate composition P
BLiquid.
Mix above-mentioned A liquid 11.8 mass parts and above-mentioned P
BLiquid 20.1 mass parts (ratio=1.0 of hydroxyl equivalent/NCO equivalent) behind the vacuum deaerator, with embodiment 7 identical ground, are made thick cured article and the surface mounting LED packaged piece of 3mm.
(comparative example 6)
As polyhydroxy reactant, in above-mentioned (A1) 12.9 mass parts, add above-mentioned (A2) 0.93 mass parts, carry out heated and stirred, form uniform polyhydroxy reactant A liquid.
On the other hand, as the polymeric polyisocyanate composition, mix above-mentioned (B6) 5.0 mass parts, above-mentioned (B5) 5.24 mass parts, (B7) 13.6 mass parts and above-mentioned (C1) 0.04 mass parts after, under reduced pressure add the heat extraction N-BUTYL ACETATE, made polymeric polyisocyanate composition B liquid.
Mix above-mentioned A liquid 13.8 mass parts and above-mentioned B liquid 19.8 mass parts (ratio=1.0 of hydroxyl equivalent/NCO equivalent), behind the vacuum deaerator,, make thick cured article and the surface mounting LED packaged piece of 3mm with embodiment 7 identical ground.
(comparative example 7)
As polyhydroxy reactant; In weight-average molecular weight: add above-mentioned (A3) 9.1 mass parts and above-mentioned (A2) 2.9 mass parts in the polycaprolactonetriol A4 of 550, hydroxyl value: 300mgKOH/g (wearing West Road chemical industrial company system, trade(brand)name " pula Ge Xier 305 "), 26.2 mass parts; Carry out heated and stirred, form uniform polyhydroxy reactant A liquid.
On the other hand, above-mentioned (A3) 1.5 mass parts are made an addition to above-mentioned (B6) 15.3 mass parts, under nitrogen atmosphere, reacted 1 hour down, made the residual prepolymer of NCO at 100 ℃.
In addition, as the polymeric polyisocyanate composition, mix above-mentioned prepolymer 16.8 mass parts, above-mentioned (B5) 16.0 mass parts, above-mentioned (B7) 41.5 mass parts, above-mentioned (C1) 0.1 mass parts after, under reduced pressure add the heat extraction N-BUTYL ACETATE, made polymeric polyisocyanate composition P
BLiquid.
Mix above-mentioned A liquid 38.2 mass parts and above-mentioned P
BLiquid 62.0 mass parts (ratio of hydroxyl equivalent/NCO equivalent=i.0), behind the vacuum deaerator,, make thick cured article and the surface mounting LED packaged piece of 3mm with embodiment 7 identical ground.
(comparative example 8)
As polyhydroxy reactant; In above-mentioned (A1) 4.9 mass parts, add weight-average molecular weight: the propylene oxide adduct A5 of the TriMethylolPropane(TMP) of 400, hydroxyl value: 400mgKOH/g (Asahi Denka Co., Ltd.'s system, trade(brand)name " T-400 ") 10.7 mass parts and above-mentioned (A2) 2.9 mass parts; Carry out heated and stirred, form uniform polyhydroxy reactant A liquid.
In addition, as the polymeric polyisocyanate composition, mix above-mentioned (B6) 5.0 mass parts, above-mentioned (B5) 5.2 mass parts, (B7) 13.6 mass parts and above-mentioned (C1) 0.04 mass parts after, under reduced pressure heat the desolventizing N-BUTYL ACETATE, made polymeric polyisocyanate composition B liquid.
Mix above-mentioned A liquid 16.5 mass parts and B liquid 19.76 mass parts (ratio=1.0 of hydroxyl equivalent/NCO equivalent), behind the vacuum deaerator,, make thick cured article and the surface mounting LED packaged piece of 3mm with embodiment 7 identical ground.
A liquid in each embodiment and each comparative example, B liquid, P
BThe use level of liquid is illustrated in table 3 and the table 4.Also have, the use level in the table is mass parts.
[table 3]
[table 4]
In addition, in above-mentioned table, A1 be weight-average molecular weight be 300 and hydroxyl value be the polycaprolactonetriol of 540mgKOH/g, A4 be weight-average molecular weight be 550 and hydroxyl value be the polycaprolactonetriol of 300mgKOH/g; A3 is a TriMethylolPropane(TMP), A5 be weight-average molecular weight be 400 and hydroxyl value be that the propylene oxide of the TriMethylolPropane(TMP) of 400mgKOH/g adds finished product, A2 be weight-average molecular weight be 500 and hydroxyl value be the polycarbonate diol of 230mgKOH/g, B6 is 4; 4 '-methylene-bis (cyclohexyl isocyanate), B5 be, 2, and 5-(2; 6) two isocyanato methyl [2,2,1] heptane, B4 is 1; Two (isocyanic ester methyl) hexanaphthenes of 3-, B7 is that B8 is the isocyanuric acid ester type polymeric polyisocyanate of hexamethylene diisocyanate as the N-BUTYL ACETATE solution of the isocyanuric acid ester type isocyanic ester 70 quality % of Trimerization of Isophorone Diisocyanate thing, C1 is 3; 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1, the 1-dimethyl ethyl]-2,4; 8,10-four oxaspiros [5,5] undecane.
About the resin combination that obtains in each embodiment and each comparative example, utilize the method shown in following to measure second-order transition temperature, thermal expansivity, bending elastic modulus.In addition, the formability the when gelation time under having estimated 165 ℃, liquid transfer mould.And then, about the surface mounting LED packaged piece, utilize the method shown in following, carry out temperature cycling test, hot and humid some lantern test.These results are illustrated in table 5 and 6.
[second-order transition temperature and thermal expansivity]
Cut out the test piece of 19mm * 3mm, thickness 3mm, utilize thermo-mechanical analysis device (trade(brand)name " TMA-8141BS TAS-100 ", physics and chemistry are learned electric corporation system), measure for 5 ℃/minute with heat-up rate.Obtain second-order transition temperature (below be called " Tg ") by the point of inflection of thermal expansion curve, obtain thermalexpansioncoefficient by the slope below the Tg
1, obtain α by the slope more than the Tg
2
[bending elastic modulus]
Cut out the test piece of 20mm * 50mm, thickness 3mm, use three point bending test device (Yin Sitelun corporate system, 5548 types), carry out pliability test, calculated bending elastic modulus by following formula based on the supported at three point that JIS-K-6911 is installed.Also have, length of support is from being 24mm, and the cross head translational speed is 0.5mm/ minute, and the mensuration temperature is to carry out under the room temperature (25 ℃).
[several 1]
[in the formula, EF: bending elastic modulus (MPa), Δ Y: addendum modification (mm), Δ P: increase the weight of (N), Lv: length of support leaves, W: the width of test piece, h: the thickness of test piece]
[gelation time]
With regard to gelation time, use gelation trier (SYSTEM SEIKO corporate system), the temperature of hot plate is set at 165 ℃, measure the time of resin solution gelation.
[liquid transfer mould property test]
The condition of molding of liquid transfer mould is a die temperature: 165～175 ℃, and sputtering pressure: 4MPa～15MPa, injection length: 20～50 seconds, the hold-time: 180～300 seconds.Utilize this method of forming, making physical dimension is the LED packaged piece shown in Figure 1 of 5.1mm * 3.9mm * 4.7mm.The outward appearance of the LED packaged piece made from microscopic examination will not confirmed to the space and will not be evaluated as " A " under the situation of filling part, with confirming to the space or not being evaluated as " C " under at least one side's of filling part the situation.
[temperature cycling test]
In temperature cycling test, use the ground manufactured samples that is described below; That is: for blue-led element; With resin solution to be equipped with physical dimension, physical dimension 3.2mm * 2.6mm * 1.8mm, die cavity internal diameter be the die cavity portion casting that gathers the packaged piece of installing on the phthalimide system case of 2.4mm (
); And be heating and curing, made the surface mounting LED packaged piece.
Test conditions with-40 ℃ following 0.5 hour, 85 ℃ following 0.5 hour be a circulation, with its carry out 500 the circulation.After test, use microscope, observe the having or not of broken string, resin and box material or chip etc. peel off have or not, the having or not etc. of the crackle of resin.Sample size is 10, confirms broken string in one, peels off or any of crackle as long as have, and just is made as " C ", does not confirm to so bad just be made as " A ".
[hot and humid some lantern test]
At first, make the electric current of DC20mA flow through above-mentioned surface mounting LED packaged piece, light LED.Use moment multichannel light measurer ianthone Da mound electronics corporation system), measure brightness L1 at this moment.Secondly, the LED packaged piece is disposed in 85 ℃, the constant temperature and humidity cabinet of 85%RH, makes the electric current of DC20mA flow through said LED packaged piece, kept 1000 hours under the state that LED is lighted.Then, the LED packaged piece is taken out from constant temperature and humidity cabinet, the electric current of DC20mA is flow through, light LED, measured brightness L2.The ratio (L2/L1) of the brightness in the constant temperature and humidity cabinet configuration front and back is made as " brightness sustainment rate "; With this brightness sustainment rate is that average evaluation more than 0.8 is " A "; With being " B " more than 0.7 and less than 0.8 average evaluation, will less than 0.7 average evaluation " C ".
[table 5]
| Project | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Second-order transition temperature (℃) | 131 | 131 | 131 | 132 |
| α1(×10 -5/℃) | 7.6 | 7.2 | 7.9 | 7.2 |
| α2(×10 -5/℃) | 18.1 | 17.6 | 18.9 | 17.9 |
| Bending elastic modulus (MPa) | 2210 | 2200 | 2210 | 2130 |
| Gelation time (second) | 150 | 170 | 150 | 120 |
| Liquid transfer mould property test | A | A | A | A |
| Temperature cycling test | A | A | A | A |
| Hot and humid some lantern test | A | A | A | A |
[table 6]
| Project | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Second-order transition temperature (℃) | 60 | 107 | 103 | 96 | 80 |
| α1(×10 -5/℃) | 7.0 | 8.6 | 8.3 | 9.4 | 11.0 |
| α2(×10 -5/℃) | 18.4 | 20.5 | 19.3 | 19.3 | 20.4 |
| Bending elastic modulus (MPa) | 2100 | 1990 | 1930 | 1800 | 1900 |
| Gelation time (second) | 95 | 130 | 190 | 260 | 720 |
| Liquid transfer mould property test | A | A | A | C | C |
| Temperature cycling test | C | C | C | C | C |
| Hot and humid some lantern test | C | A | A | A | A |
As shown in table 5, in embodiment 7～10, second-order transition temperature is more than 110 ℃, and α 1 is 10 * 10
-5/ ℃ below, α 2 is 20 * 10
-5/ ℃ below, do not found the broken string in the temperature cycling test or peeled off etc. bad, clear and definite that heatproof degree cyclicity is superior.In addition, all do not found the significantly reduction of hot and humid the brightness in the lantern test or peeled off etc. bad, clear and definite that high-temp resisting high-humidity resisting property is also superior.
On the other hand, as shown in table 6, second-order transition temperature is low, does not contain in the comparative example 4 that has with the polymeric polyisocyanate of secondary carbon bonded NCO, in temperature cycling test, the broken string of metal wire takes place, and the brightness in hot and humid some lantern test reduces big.Equally, in comparative example 5～8, second-order transition temperature is all low, therefore, the broken string of metal wire has taken place.
Utilizability on the industry
Like above explanation, can know according to the present invention, the curable resin composition that especially can form the superior fully cured article of high-temp resisting high-humidity resisting property, LED packaged piece and the method for manufacture thereof of using said resin combination to make can be provided.In addition, can know, can provide to form transparency height according to the present invention; Fast light, heat-resisting optical characteristics such as painted or mechanical characteristics are superior; Simultaneously, second-order transition temperature is high, and the curable resin composition of the low cured article of thermal expansivity, uses the photosemiconductor of its making.
Claims (13)
1. curable resin composition, wherein, contain:
Polyhydroxy reactant;
The polymeric polyisocyanate composition, it contains the chemical structure that NCO is incorporated into secondary carbon(atom) and has the isocyanuric acid ester type isocyanic ester more than more than one two functional groups,
The second-order transition temperature of the cured article of said curable resin composition is more than 110 ℃, and the thermal expansivity when second-order transition temperature is following is 10.0 * 10
-5/ ℃ below, the thermal expansivity when second-order transition temperature is above is 20.0 * 10
-5/ ℃ below, and the bending elastic modulus under 25 ℃ is more than the 1500MPa,
Said polyhydroxy reactant is so that to contain weight-average molecular weight more than the 40 quality % be below 500 and hydroxyl value is the polycaprolactone polyol more than the trifunctional more than the 300mgKOH/g; And so that to contain weight-average molecular weight more than the 30 quality % be below 350 and hydroxyl value is the aliphatic polyol more than the trifunctional more than the 500mgKOH/g
Said polymeric polyisocyanate composition is to contain said isocyanuric acid ester type isocyanic ester more than the 40 quality %.
2. curable resin composition according to claim 1, wherein,
Said aliphatic polyol is the TriMethylolPropane(TMP) or derivatives thereof.
3. curable resin composition according to claim 1 and 2, wherein,
Said isocyanuric acid ester type isocyanic ester is the Trimerization of Isophorone Diisocyanate thing.
4. curable resin composition according to claim 1 and 2, wherein,
Said polyhydroxy reactant contains: make obtain, the residual prepolymer that hydroxyl is arranged of isocyanate reaction more than two functional groups of NCO of the sum that polyvalent alcohol and the sum with the hydroxyl that has than this polyvalent alcohol lack.
5. curable resin composition according to claim 4, wherein,
Said prepolymer in the said polyhydroxy reactant is that to make the ratio (X/Y) of the NCO equivalent Y in said polyvalent alcohol and the hydroxyl equivalent X of said isocyanic ester in said polyvalent alcohol and the said isocyanic ester be that reaction obtains under the condition more than 3.
6. curable resin composition according to claim 1 and 2, wherein,
Said polymeric polyisocyanate composition contains: obtain, the residual prepolymer that NCO is arranged of polyol reaction that makes the hydroxyl of the sum that above isocyanic ester of two functional groups and the sum with the NCO that has than this isocyanic ester lack.
7. curable resin composition according to claim 6, wherein,
Said polyvalent alcohol is that weight-average molecular weight is below 350 and hydroxyl value is the above aliphatic polyol of the above trifunctional of 500mgKOH/g.
8. curable resin composition according to claim 6, wherein,
Said prepolymer in the said polymeric polyisocyanate composition is that to make the ratio (X/Y) of the NCO equivalent Y in said polyvalent alcohol and the hydroxyl equivalent X of said isocyanic ester in said polyvalent alcohol and the said isocyanic ester be to react under 0.05～0.30 the condition to obtain.
9. curable resin composition according to claim 1 and 2, wherein,
Contain: the type phenol of being obstructed is inhibitor.
10. curable resin composition according to claim 9, wherein,
The said type phenol that is obstructed is that inhibitor is 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyl group }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.
11. curable resin composition according to claim 1 and 2, wherein,
Gelation time under 165 ℃ is 10～200 seconds.
12. according to claim 1 or 2 gained curable resin compositions, wherein,
So that the ratio of the NCO equivalent in the hydroxyl equivalent in the said polyhydroxy reactant and the said polymeric polyisocyanate composition, promptly the ratio of hydroxyl equivalent/NCO equivalent becomes 0.7～1.3 mode and contains said polyhydroxy reactant and said polymeric polyisocyanate composition.
13. a photosemiconductor wherein, possesses:
Utilize liquid transfer moudling, each described curable resin composition in the claim 1～12 is carried out the parts that moulding obtains.
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|---|---|---|---|
| JP114148/2007 | 2007-04-24 | ||
| JP2007114149 | 2007-04-24 | ||
| JP2007114148 | 2007-04-24 | ||
| JP114149/2007 | 2007-04-24 | ||
| JP2007282031 | 2007-10-30 | ||
| JP282031/2007 | 2007-10-30 | ||
| PCT/JP2008/057840 WO2008133271A1 (en) | 2007-04-24 | 2008-04-23 | Curable resin composition, led package, and method for production of the led package, and optical semiconductor |
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| CN101668786B true CN101668786B (en) | 2012-12-05 |
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| EP (1) | EP2141185A4 (en) |
| JP (1) | JP5327047B2 (en) |
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| JP5277940B2 (en) * | 2008-09-29 | 2013-08-28 | 日立化成株式会社 | Curable resin composition, LED package, and manufacturing method thereof |
| JP5417910B2 (en) * | 2008-10-16 | 2014-02-19 | 日立化成株式会社 | Urethane resin composition and optical semiconductor device |
| WO2011043090A1 (en) | 2009-10-05 | 2011-04-14 | 日立化成工業株式会社 | Urethane resin composition, cured object, and photosemiconductor device using cured object |
| CN102219991B (en) * | 2010-04-15 | 2013-02-27 | 林宏泰 | Method for manufacturing polyurethane (PU) resin material capable of emitting light |
| JP5893874B2 (en) | 2011-09-02 | 2016-03-23 | 信越化学工業株式会社 | Optical semiconductor device |
| JP6563194B2 (en) * | 2012-11-05 | 2019-08-21 | ソニーセミコンダクタソリューションズ株式会社 | Optical device manufacturing method |
| TWI616489B (en) | 2013-02-18 | 2018-03-01 | Polysiloxane composition, base formula applicable to light-emitting diode element and light-emitting diode element thereof | |
| CN103627163A (en) * | 2013-09-10 | 2014-03-12 | 上纬企业股份有限公司 | LED (Light Emitting Diode) packaging polyurethane resin composition |
| KR101938949B1 (en) * | 2013-12-23 | 2019-01-15 | 인텔 코포레이션 | Package on package architecture and method for making |
| TWI572633B (en) * | 2014-05-02 | 2017-03-01 | Asahi Kasei Chemicals Corp | Polyisocyanate hardening, and polyisocyanate hardening |
| US9641163B2 (en) | 2014-05-28 | 2017-05-02 | Cree, Inc. | Bandwidth limiting methods for GaN power transistors |
| US9515011B2 (en) | 2014-05-28 | 2016-12-06 | Cree, Inc. | Over-mold plastic packaged wide band-gap power transistors and MMICS |
| US9472480B2 (en) * | 2014-05-28 | 2016-10-18 | Cree, Inc. | Over-mold packaging for wide band-gap semiconductor devices |
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| DE102017123342A1 (en) * | 2017-10-09 | 2019-04-11 | Schott Ag | TO housing with high reflection loss |
| CN111171688A (en) * | 2018-11-12 | 2020-05-19 | 湖南航天三丰科工有限公司 | Wind power blade edge protection paint based on bio-based polyol |
| CN111205462B (en) * | 2020-01-10 | 2021-03-30 | 山东大学 | Preparation method of silicone resin containing perfluor cyclobutyl aryl ether structure |
| CN116463049B (en) * | 2023-03-29 | 2023-10-17 | 湖南聚仁化工新材料科技有限公司 | Photo-curing dual-curing coating |
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| US20100200890A1 (en) | 2010-08-12 |
| WO2008133271A1 (en) | 2008-11-06 |
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| TWI373478B (en) | 2012-10-01 |
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| JP5327047B2 (en) | 2013-10-30 |
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| KR101175836B1 (en) | 2012-08-24 |
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